Chemistry Commons^™

Comparative Study On The Flammability Of Polyethylene Modified With Commercial Fire Retardants And A Zinc Aluminum Oleate Layered Double Hydroxide, Charles Manzi-Nshuti, Jeanne Hossenlopp, Charles A. Wilkie

Chemistry Faculty Research and Publications

Polyethylene (PE) was modified by the addition of a layered hydroxide of zinc aluminum oleate (ZnAl) and/or commercial fire retardants. Commercial additives included: melamine polyphosphate (MPP), ammonium polyphosphate (APP), triphenol phosphate (TPP), resorcinol diphosphate (RDP), decabromophenyl oxide (DECA) and antimony oxide (AO). The thermal stability and the combustion behaviors of the new composite polymeric materials are evaluated in TGA experiments and cone calorimetry. At 20% total additive loading, APP and LDH enhance the thermal stability of the PE composites and favor char formation. ZnAl leads to the best reduction in the peak of heat release rate (PHRR), 72%, while the …

Variation Of Anions In Layered Double Hydroxides: Effects On Dispersion And Fire Properties, Linjiang Wang, Shengpei Shu, Dan Chen, Charles A. Wilkie

Chemistry Faculty Research and Publications

Layered double hydroxides (LDHs) are interesting materials for nanocomposite formation because one can vary the identity of the metals, the anions and the stoichiometry to see the effect of these on the ability of the nano-material to disperse in a polymer and to see what effect dispersion has on the properties of the polymer. In this study, the anions 2-ethylhexyl sulfate (SEHS), bis(2-ethylhexyl) phosphate (HDEHP) and dodecyl benzenesulfonate (SDBS) have been utilized as the charge balancing anions to synthesize organo-LDHs. Nanocomposites of poly(methyl methacrylate) (PMMA) and polystyrene (PS) with organo-LDHs were prepared both by melt blending and bulk polymerization. X-ray …

1,2-Dimethyl-4,5-Diphenylbenzene Determined On A Bruker Smart X2s Benchtop Crystallographic System, Jonathan B. Briggs, Mikael D. Jazdzyk, Glen P. Miller

Chemistry

The title compound, C(20)H(18), has two crystallographically independent molecules in the asymmetric unit. The phenyl substituents of molecule A are twisted away from the plane defined by the central benzene ring by 131.8 (2) and -52.7 (3)degrees. The phenyl substituents of molecule B are twisted by -133.3 (2) and 50.9 (3)degrees. Each molecule is stabilized by a pair of intraMolecular C(aryl, sp(2))-H center dot center dot center dot pi interactions, as well as by several interMolecular C(methyl, sp(3))-H center dot center dot center dot pi interactions.

Information-Theoretical Analysis Of Time-Correlated Single-Photon Counting Measurements Of Single Molecules, David Talaga

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Time-correlated single photon counting allows luminescence lifetime information to be determined on a single molecule level. This paper develops a formalism to allow information theory analysis of the ability of luminescence lifetime measurements to resolve states in a single molecule. It analyzes the information content of the photon stream and the fraction of that information that is relevant to the state determination problem. Experimental losses of information due to instrument response, digitization, and different types of background are calculated and a procedure to determine the optimal value of experimental parameters is demonstrated. This paper shows how to use the information …

Spectroscopic Characterizations Of The Compound Ii Intermediate Of Soybean Peroxidase From Soybean Seed Coatings, Andoh-Baidoo Rosemarie Agyepong

Theses and Dissertations

Spectroscopic characterization of ferric soybean peroxidase with peroxides were studied to determine the ligand coordination and to characterize the structure of the heme active site and its intermediates (ferryl species). The lifetime, chemical reactivity and distinctive colors of the ferryl species (FeIV) formed during the oxidation of peroxidase (FeIII) by peroxides enabled structure, dynamics and reaction mechanisms to be studied. Resonance Raman spectroscopy was used as a means of characterizing the structure of the soybean peroxidase and its intermediates. Excitation in the Soret absorption band at 406.7nm with 2-5mW laser power was used for this study. Resonance Raman spectra in …

Adsorption Of Co On Supported Gold Nanoparticle Catalysts: A Comparative Study, Heather Hartshorn, Christopher J. Pursell, Bert D. Chandler

Chemistry Faculty Research

The adsorption of CO on three different gold nanoparticle catalysts supported on high surface area TiO₂ was studied using infrared transmission spectroscopy at room temperature and CO pressures typically used in CO oxidation reactions. The three, real-world catalysts were Au catalysts synthesized in our laboratory from thiol monolayer protected clusters (MPCs) and two commercial catalysts from the World Gold Council (WGC and AuTEK). Within experimental reproducibility, the adsorption data for the three catalysts are indistinguishable. While showing approximately Langmuir behavior, the adsorption data also show coverage dependence, as others have observed for many catalyst systems. Two approaches were used …

Ionic Selectivity In L-Type Calcium Channels By Electrostatics And Hard-Core Repulsion, Dezso Boda, Douglas Henderson, Monika Valisko, Bob Eisenberg, Dirk Gillespie

Faculty Publications

A physical model of selective "ion binding" in the L-type calcium channel is constructed, and consequences of the model are compared with experimental data. This reduced model treats only ions and the carboxylate oxygens of the EEEE locus explicitly and restricts interactions to hard-core repulsion and ion–ion and ion–dielectric electrostatic forces. The structural atoms provide a flexible environment for passing cations, thus resulting in a self-organized induced-fit model of the selectivity filter. Experimental conditions involving binary mixtures of alkali and/or alkaline earth metal ions are computed using equilibrium Monte Carlo simulations in the grand canonical ensemble. The model pore rejects …

Accelerated Oxidation Of Epinephrine By Silica Nanoparticles, Zhimin Tao, Gang Wang, Jerry Goodisman, Tewodros Asefa

Chemistry - All Scholarship

We have measured the influence of mesoporous silica (MCM-41 and SBA-15) nanoparticles and dense silica nanoparticles on epinephrine oxidation, a pH-dependent reaction, whose rate is small in acidic or neutral solutions but much greater at higher pH. The reaction was measured by monitoring adrenochrome at 480 nm, the product of epinephrine oxidation. In distilled water (dH ₂O) with no particles present, the oxidation of epinephrine occurs slowly but more rapidly at higher pH. The presence of MCM-41 or silica spheres does not accelerate the oxidation, but SBA-15 does, showing that the difference in the structures of nanomaterials leads to …

The Separation And Indentification Of Polyoxometalate Mixtures, Stephanie Peterson

Honors Capstones

Capstone submitted as a graduate requirement for the BSU Honors Program.

Liquid Carbon Dioxide Extraction Of Various Food Flavors: Evaluation And Analysis, Deven Lee Shinholt

Undergraduate Honors Thesis Collection

Sub- and supercritical carbon dioxide has been utilized as an extraction solvent for a variety of natural compounds. This requires the use of specialized high-pressure vessels. It was reported recently that common laboratory apparatus (centrifuge tubes) could be utilized in liquid carbon dioxide extractions obviating the need for specialized equipment. Various herbs and spices (including orange, lemon, lime, and grapefruit zest, oregano, rosemary, sage, spearmint, nutmeg, black peppercorns, cloves, caraway seeds, and vanilla beans) were used as substrates for liquid carbon dioxide extractions by this straightforward technique. The extracted oils, containing terpenes and terpenoids, were then analyzed through GC/MS. Liquid …

The Rotational Spectrum Of The Fed Radical In Its X4Δ State, Measured By Far-Infrared Laser Magnetic Resonance, Michael Jackson, Lyndon R. Zink, Jonathan P. Towle, Neil Riley, John M. Brown

All Faculty Scholarship for the College of the Sciences

Transitions between the spin-rotational levels of the FeD radical in the v = 0level of the X ⁴Δ ground state have been detected by the technique of laser magnetic resonance at far-infrared wavelengths. Pure-rotational transitions have been observed for the three lowest spin components. Lambda-type doubling is resolved on all the observed transitions; nuclear hyperfine structure is not observed. The energy levels of FeD are strongly affected by the breakdown of the Born–Oppenheimer approximation and cannot be modeled accurately by an effective Hamiltonian. The data are therefore fitted to an empirical formula to yield term values and g-factors for …

Synthesis Of 2,4,5-Triaminocyclohexane Carboxylic Acid As A Novel 2-Deoxystreptamine Mimetic, Sarah Elizabeth Roberts

Theses and Dissertations

RNAs have become increasingly recognized as possible drug targets due to their involvement in important biochemical functions, as well as their unique but well-defined structures. Recently published crystal structures depict the binding of a series of aminoglycosides- or more specifically- 2-deoxystretamine (2-DOS), the most preserved central scaffold of aminoglycosides, to a conserved 5'-GU-3'region on their target RNAs. A novel unnatural γ-amino acid, 1, has been synthesized using 2-deoxystreptamine as a template through structure-based rational design. The unnatural amino acid has been designed to replace a glycosidic linkage with an amide bond, which may limit the promiscuous binding characteristics of aminoglycosides …

Ccsd(T) Complete Basis Set Limit Relative Energies For Low-Lying Water Hexamer Structures, Desiree M. Bates, Gregory S. Tschumper

Chemistry Faculty Research & Creative Works

MP2 and CCSD(T) complete basis set (CBS) limit relative electronic energies (ΔE e) have been determined for eight low-lying structures of the water hexamer by combining explicitly correlated MP2-R12 computations with higher-order correlation corrections from CCSD(T) calculations. Higher-order correlation effects are quite substantial and increase ΔE e by at least +0.19 kcalmol^-1 and as much as +0.59 kcalmol^-1. The effects from zero-point vibrational energy (ZPVE) have been assessed from unsealed harmonic vibrational frequencies computed at the MP2 level with a correlation consistent triple-̌ basis set (cc-pVTZ for H and aug-cc-pVTZ for O). ZPVE effects are even more …

Structure–Mutagenicity Relationships And Energies Of 1-, And 2-Nitrotriphenylenes [Abstract], Kefa Karimu Onchoke

Faculty Publications

No abstract provided.

Subunit-Selective Interrogation Of Co Recombination In Carbonmonoxy Hemoglobin By Isotope-Edited Time-Resolved Resonance Raman Spectroscopy, Gurusamy Balakrishnan, Xiaojie Zhao, Edyta Podstawska, Leonard M. Proniewicz, James R. Kincaid, Thomas G. Spiro

Chemistry Faculty Research and Publications

Hemoglobin (Hb) is an allosteric tetrameric protein made up of αβ heterodimers. The α and β chains are similar, but are chemically and structurally distinct. To investigate dynamical differences between the chains, we have prepared tetramers in which the chains are isotopically distinguishable, via reconstitution with ¹⁵N-heme. Ligand recombination and heme structural evolution, following HbCO dissociation, was monitored with chain selectivity by resonance Raman (RR) spectroscopy. For α but not for β chains, the frequency of the ν₄ porphyrin breathing mode increased on the microsecond time scale. This increase is a manifestation of proximal tension in the Hb …

Nano-Imprinted Thin Films Of Reactive, Azlactone-Containing Polymers: Combining Methods For The Topographic Patterning Of Cell Substrates With Opportunities For Facile Post-Fabrication Chemical Functionalization, Nathaniel J. Fredin, Adam H. Broderick, Maren E. Buck, David M. Lvnn

Chemistry: Faculty Publications

Approaches to the fabrication of surfaces that combine methods for the topographic patterning of soft materials with opportunities for facile, post-fabrication chemical functionalization could contribute significantly to advances in biotechnology and a broad range of other areas. Here, we report methods that can be used to introduce well defined nano- and microscale topographic features to thin films of reactive polymers containing azlactone functionality using nanoimprint lithography (NIL). We demonstrate that NIL can be used to imprint topographic patterns into thin films of poly(2-vinyl-4,4- dimethylazlactone) and a copolymer of methyl methacrylate and 2-vinyl- 4,4-dimethylazlactone using silicon masters having patterns of grooves …

The Scope And Limitations Of Intramolecular Nicholas And Pauson-Khand Reactions For The Synthesis Of Tricyclic Oxygen- And Nitrogen-Containing Heterocycles, Kristina D. Closser, Miriam M. Quintal, Kevin M. Shea

Chemistry: Faculty Publications

We studied the scope and limitations of a tandem intramolecular Nicholas/Pauson−Khand strategy for the synthesis of tricyclic oxygen- and nitrogen-containing heterocycles. This methodology enables conversion of simple acyclic starting materials into a series of previously unknown heterocyclic architectures. For the preparation of cyclic ethers (Z = O), tricyclic [5,6,5]- through [5,9,5]-systems (m = 1, n = 1−4) are available with the [5,7,5]- and [5,8,5]-systems amenable to quick and efficient synthesis. Tricyclic [5,7,5]- and [5,8,5]-amine-containing (Z = NTs) heterocycles can be successfully prepared. Attempts to make larger ring systems (Z = O, m = 2; Z = O, n = …

Universal Scaling Of Nonequilibrium Transport In The Kondo Regime Of Single Molecule Devices, G D. Scott, Z K. Keane, Jacob W. Ciszek, J M. Tour, D Natelson

Chemistry: Faculty Publications and Other Works

Scaling laws and universality are often associated with systems exhibiting emergent phenomena possessing a characteristic energy scale. We report nonequilibrium transport measurements on two different types of single molecule transistor devices in the Kondo regime. The conductance at low bias and temperature adheres to a scaling function characterized by two parameters. This result, analogous to that reported recently in semiconductor dots with Kondo temperatures two orders of magnitude lower, demonstrates the universality of this scaling form. We compare the extracted values of the scaling coefficients to previous experimental and theoretical results.

Material Properties Of Nanoclay Pvc Composites, Walid Awad, Gunter Beyer, Daphne Benderly, Wouter L. Ijdo, Ponusa Songtipya, Maria Del Mar Jimenez-Gasco, Evangelos Manias, Charles A. Wilkie

Chemistry Faculty Research and Publications

Nanocomposites of poly(vinyl chloride) have been prepared using both hectorite- and bentonite-based organically-modified clays. The organic modification used is tallow-triethanol-ammonium ion. The morphology of the systems was investigated using X-ray diffraction and transmission electron microscopy and these systems show that true nanocomposites, both intercalated and exfoliated systems, are produced. The mechanical properties have been evaluated and the modulus increases upon nanocomposite formation without a significant decrease in tensile strength or elongation at break. Thermal analysis studies using thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis were conducted. Thermal stability of the PVC systems was assessed using a standard thermal …

Controlled Assembly Of Rodlike Viruses With Polymers, Tao Li, Laying Wu, Nisaraporn Suthiwangcharoen, Michael A. Bruckman, Dayton Cash, Joan S. Hudson, Soumitra Ghoshroy, Qian Wang

Faculty Publications

A practical method to assemble rodlike tobacco mosaic virus and bacteriophage M13 with polymers was developed, which afforded a 3D core–shell composite with morphological control.

Role Of Molecular Chaperones In G Protein B5-Regulator Of G Protein Signaling Dimer Assembly And G Protein By Dimer Specificity, Alyson Cerny Howlett

Theses and Dissertations

In order for G protein signaling to occur, the G protein heterotrimer must be assembled from its nascent polypeptides. The most difficult step in this process is the formation of the Gβγ dimer from the free subunits since both are unstable in the absence of the other. Recent studies have shown that phosducin-like protein (PhLP1) works as a co-chaperone with the cytosolic chaperonin complex (CCT) to fold Gβ and mediate its interaction with Gγ. However, these studies did not address questions concerning the scope of PhLP1 and CCT-mediated Gβγ assembly, which are important questions given that there are four Gβs …

Aqueous Phase C-H Bond Oxidation Reaction Of Arylalkanes Catalyzed By A Water-Soluble Cationic Ru(Iii) Complex [(Pymox-Me2)2Rucl2]+Bf4-, Chae S. Yi, Ki Hyeok Kwon, Do W. Lee

Chemistry Faculty Research and Publications

The cationic complex [(pymox-Me₂)RuCl₂]⁺BF₄⁻ was found to be a highly effective catalyst for the C−H bond oxidation reaction of arylalkanes in water. For example, the treatment of ethylbenzene (1.0 mmol) with t-BuOOH (3.0 mmol) and 1.0 mol % of the Ru catalyst in water (3 mL) cleanly produced PhCOCH₃ at room temperature. Both a large kinetic isotope effect (k_H/k_D = 14) and a relatively large Hammett value (ρ = −1.1) suggest a solvent-caged oxygen rebounding mechanism via a Ru(IV)-oxo intermediate species.

Visualizing Atomic Orbitals Using Second Life, Andrew Lang, David C. Kobilnyk

College of Science and Engineering Faculty Research and Scholarship

No abstract provided.

Visualizing Atomic Orbitals Using Second Life, Andrew Lang, David C. Kobilnyk

College of Science and Engineering Faculty Research and Scholarship

We demonstrate the usefulness of Second Life as a platform for enlivening major concepts in chemistry education. These concepts include absorption spectra, selection rules, quantum numbers, and atomic orbital shapes. We have built several exhibits in Second Life which provide 3-dimensional interactivity for each of those areas: an interactive experiment showing the absorption spectrum of hydrogen, an interactive model of selection rules showing allowed and forbidden transitions for each state, a 3-dimensional grid of orbitals showing the constraints on the values of quantum numbers, and a large-scale interactive orbital display allowing the user to choose and rotate to-scale atomic orbitals …

Pat Proteins, An Ancient Family Of Lipid Droplet Proteins That Regulate Cellular Lipid Stores. Biochim Biophys Acta, John Tansey

Chemistry Faculty Scholarship

The PAT family of lipid droplet proteins includes 5 members in mammals: perilipin, adipose differentiation-related protein (ADRP), tail-interacting protein of 47 kiloDaltons (TIP47), S3-12, and OXPAT. Members of this family are also present in evolutionarily distant organisms, including insects, slime molds and fungi. All PAT proteins share sequence similarity and the ability to bind intracellular lipid droplets, either constitutively or in response to metabolic stimuli, such as increased lipid flux into or out of lipid droplets. Positioned at the lipid droplet surface, PAT proteins manage access of other proteins (lipases) to the lipid esters within the lipid droplet core and …

Activation Energy Of The Formation Of The Allylic Carbocation In The Acid Catalyzed Dehydration Of 4-Methylcyclohexanol, Dequina Nicholas

Capstone Research Projects

The existence of a persisting allylic compound at equilibrium of the dehydration of 4-methyl cyclohexanol in 80% w/w sulfuric acid is supported by absorbance vs. time plots from UV-vis analysis . The peak seen at 305 nm is an indication of the formation of an allylic carbocation over time and therefore can support a proposed mechanism for this reaction. Kinetic analysis of the compound at 35.0°C, 48.5°C, 60.0°C, and 66.8°C shows that the dehydration reaction is first order with rate constants of 1.83 x 10-5s-1 , 1.27 x 10-4s-1 , 9.28x10-4s-1, and 9.55x10-4s-1 respectively for each temperature and an activation …

An Attempt To Reduce 2-Methyl-1, 4-Naphthalenedione (Menadione) To 1, 4-Dihydro-2- Methyl-1, 4-Naphthalenediol, Alexandria S. Cooke

Capstone Research Projects

In the following report, menadione is used as the starting material of a multi-step Aldol synthesis to yield a derivative. Menadione, a known precursor of vitamin K., is proposed to be combined with safranal, from the saffron plant, to generate a product with possible benefits in the food and medical industries. The target derivative compound is a highly conjugated structure with three 6-membered rings. Current findings show that menadione is highly insoluble in water and difficult to hydrate using a typical acid and water hydration method. Hydration was attempted and unsuccessful withH3PO4 and H2SO4, thus a new method was implemented. …

Pictorial Quantum Chemistry, Theory And Application Of Valency Interaction Formulas, Vif, Joseph D. Alia

Chemistry Publications

No abstract provided.

Chemistry & Biochemistry Newsletter, Department Of Chemistry & Biochemistry, South Dakota State University

Chemistry & Biochemistry Newsletter: 2002-2015

Inside:

Page 2 Two majors win Schultz-Werth Awards

Page 3 Building Update

Page 4 Nagyvary is Lardy Lecture speaker; Raynie Gives Earth Day Talk; Logue Work Recognized; Grad student joins Young Chemists in Cancer Research committee

Page 5 Pravecek retires from Clinical Laboratory Teaching; Chem Grad student selected for national conference

Page 6 2008-2009 Chemistry and Biochemistry Graduates

Page 7 New Research Center Will Find New Uses for Light; Tanaka Undergraduate Award

Page 8 Scholarships and Award Winners

Potential Role Of Micro-Algae On Global Energy Supply, Sage Callaway-Keeley, Stephanie Huynh

Student Research Posters

The most effective ways to reduce CO2 emissions are to improve the energy efficiency of each economic sector and to reduce the cutting of tropical and temperate forests around the world. These options, however, may not fully reach their technical and economic potential due to various political and socioeconomic. The most practical of these is to increase CO2 sinks through photosynthesis in both standing tree biomass and in ocean primary producers. The use of marine algae as CO2 sinks is for large-scale CO2 mitigation: the use of phytoplankton through Fe fertilization and macro algal (kelp) farms, which can be used …